EP2073276B1

EP2073276B1 - Exponentially doped layers in inverted metamorphic multijunction solar cells

Info

Publication number: EP2073276B1
Application number: EP08021551.0A
Authority: EP
Inventors: Mark A Stan; Arthur Cornfield; Vance Ley
Original assignee: Solaero Technologies Corp
Current assignee: Solaero Technologies Corp
Priority date: 2007-12-13
Filing date: 2008-12-11
Publication date: 2018-11-21
Anticipated expiration: 2028-12-11
Also published as: TW200926426A; JP5456923B2; JP5318522B2; US7727795B2; CN101459204A; US20090155952A1; TWI355091B; JP2009147309A; EP2073276A2; JP2013165299A; EP2073276B8; US20090155951A1; EP2073276A3

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the field of solar cell semiconductor devices, and particularly to multijunction solar cells including a metamorphic layer. Such devices also include solar cells known as inverted metamorphic solar cells.

a. Description of the Related Art

Photovoltaic cells, also called solar cells, are one of the most important new energy sources that have become available in the past several years. Considerable effort has gone into solar cell development. As a result, solar cells are currently being used in a number of commercial and consumer-oriented applications. While significant progress has been made in this area, the requirement for solar cells to meet the needs of more sophisticated applications has not kept pace with demand. Applications such as satellites used in data communications have dramatically increased the demand for solar cells with improved power and energy conversion characteristics.
In satellite and other space related applications, the size, mass and cost of a satellite power system are dependent on the power and energy conversion efficiency of the solar cells used. Putting it another way, the size of the payload and the availability of on-board services are proportional to the amount of power provided. Thus, as the payloads become more sophisticated, solar cells, which act as the power conversion devices for the on-board power systems, become increasingly more important.
Solar cells are often fabricated in vertical, multijunction structures, and disposed in horizontal arrays, with the individual solar cells connected together in a series. The shape and structure of an array, as well as the number of cells it contains, are determined in part by the desired output voltage and current.
Inverted metamorphic solar cell structures such as described in US 2004/166681 A1 , in EP 1 863 099 A2 , or in M.W. Wanless et al., Lattice Mismatched Approaches for High Performance, III - V Photovoltaic Energy Converters (Conference Proceedings of the 31st IEEE Photovoltaic Specialists Conference, Jan. 3-7, 2005, IEEE Press, 2005) present an important starting point for the development of future commercial high efficiency solar cells. The structures described in such prior art present a number of practical difficulties relating to the appropriate choice of materials and fabrication steps.
Prior to the present invention, the materials and fabrication steps disclosed in the prior art have not been adequate to produce a commercially viable and energy efficient solar cell using an inverted metamorphic cell structure.

SUMMARY OF THE INVENTION

The present invention is defined in claim 1. The present invention provides a method of forming a multijunction solar cell comprising an upper subcell, a middle subcell, and a lower subcell, the method comprising: providing first substrate for the epitaxial growth of semiconductor material; forming a first solar subcell having a base and an emitter on said substrate having a first band gap; forming a second solar subcell having a base and an emitter over said first solar subcell having a second band gap smaller than said first band gap; forming a grading interlayer over said second subcell, said grading interlayer having a third band gap greater than said second band gap; and forming a third solar subcell having a base and an emitter over said grading interlayer having a fourth band gap smaller than said second band gap such that said third subcell is lattice mis-matched with respect to said second subcell, wherein at least the base of the lower subcell has an exponentially doped profile.
In another aspect, the present invention provides a method of manufacturing a solar cell by providing a first substrate, depositing on the first substrate a sequence of layers of semiconductor material forming a solar cell, including at least the base of the lower subcell with exponential doping; mounting a surrogate substrate on top of the sequence of layers; and removing the first substrate.
In another aspect, the present invention provides a method for forming a solar cell comprising forming a top cell including base and emitter layers composed of InGaP semiconductor material; forming a middle cell emitter layer of InGaP semiconductor material and a base layer of GaAs semiconductor material; and forming a bottom cell including an emitter and base layer of InGaAs semiconductor material, wherein at least the base of the bottom cell has an exponentially doped profile.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be better and more fully appreciated by reference to the following detailed description when considered in conjunction with the accompanying drawings, wherein

FIG. 1 is an enlarged cross-sectional view of a solar cell constructed according to the present invention;
FIG. 2 is a cross-sectional view of the solar cell of FIG. 1 after the next process step;
FIG. 3 is a cross-sectional view of the solar cell of FIG. 2 after the next process step;
FIG. 4 is a cross-sectional view of the solar cell of FIG. 3 after the next process step;
FIG. 5A is a cross-sectional view of the solar cell of FIG. 4 after the next process step in which the original substrate is removed;
FIG. 5B is another cross-sectional view of the solar cell of FIG. 5A with the surrogate substrate on the bottom of the Figure;
FIG. 6A is a top plan view of a wafer in which the solar cells are fabricated;
FIG. 6B is a bottom plan view of a wafer in which the solar cells are fabricated;
FIG. 7 is a top plan view of the wafer of FIG. 6A after the next process step;
FIG. 8 is a cross-sectional view of the solar cell of FIG. 5B after the next process step;
FIG. 9 is a cross-sectional view of the solar cell of FIG. 8 after the next process step;
FIG. 10 is a cross-sectional view of the solar cell of FIG. 9 after the next process step;
FIG. 11 is a cross-sectional view of the solar cell of FIG. 10 after the next process step;
FIG. 12 is a cross-sectional view of the solar cell of FIG. 11 after the next process step;
FIG. 13 is a cross-sectional view of the solar cell of FIG. 12 after the next process step;
FIG. 14 is a cross-sectional view of the solar cell of FIG. 13 after the next process step;
FIG. 15 is a cross-sectional view of the solar cell of FIG. 14 after the next process step;
FIG. 16 is a graph of the doping profile between the emitter and base layer in a subcell of the inverted metamorphic solar cell not forming part of the present invention.

DESCRIPTION OF THE PRIOR ART AND PREFERRED EMBODIMENT

Details of the present invention will now be described including exemplary aspects and embodiments thereof. Referring to the drawings and the following description, like reference numbers are used to identify like or functionally similar elements, and are intended to illustrate major features of exemplary embodiments in a highly simplified diagrammatic manner. Moreover, the drawings are not intended to depict every feature of the actual embodiment nor the relative dimensions of the depicted elements, and are not drawn to scale.
FIG. 1 depicts the multijunction solar cell according to the present invention after formation of the three subcells A, B and C on a substrate. More particularly, there is shown a substrate 101, which may be either gallium arsenide (GaAs), germanium (Ge), or other suitable material. In the case of a Ge substrate, a nucleation layer 102 is deposited on the substrate. On the substrate, or over the nucleation layer 102, a buffer layer 103, and an etch stop layer 104 are further deposited. A contact layer 105 is then deposited on layer 104, and a window layer 106 is deposited on the contact layer. The subcell A, consisting of an n+ emitter layer 107 and a p-type base layer 108, is then deposited on the window layer 106.
It should be noted that the multijunction solar cell structure could be formed by any suitable combination of group III to V elements listed in the periodic table subject to lattice constant and band gap requirements, wherein the group III includes boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (T). The group IV includes carbon (C), silicon (Si), germanium (Ge), and tin (Sn). The group V includes nitrogen (N), phosphorous (P), arsenic (As), antimony (Sb), and bismuth (Bi).
In the preferred embodiment, the emitter layer 107 is composed of InGa(Al)P and the base layer 108 is composed of InGa(Al)P. The aluminum or Al term in parenthesis in the preceding formula means that Al is an optional constituent, and in this instance may be used in an amount ranging from 0% to 30%.
On top of the base layer 108 is deposited a back surface field ("BSF") layer 109 used to reduce recombination loss.
The BSF layer 109 drives minority carriers from the region near the base/BSF interface surface to minimize the effect of recombination loss. In other words, a BSF layer 109 reduces recombination loss at the backside of the solar subcell A and thereby reduces the recombination in the base.
On top of the BSF layer 109 is deposited a sequence of heavily doped p-type and n-type layers 110 which forms a tunnel diode which is a circuit element to connect subcell A to subcell
On top of the tunnel diode layers 110 a window layer 111 is deposited. The window layer 111 used in the subcell B also operates to reduce the recombination loss. The window layer 111 also improves the passivation of the cell surface of the underlying junctions. It should be apparent to one skilled in the art, that additional layer(s) may be added or deleted in the cell structure without departing from the scope of the present invention.
On top of the window layer 111 the layers of subcell B are deposited: the emitter layer 112, and the p-type base layer 113. These layers are preferably composed of InGaP and In_0.015GaAs respectively, (for a Ge growth template) although any other suitable materials consistent with lattice constant and band gap requirements may be used as well.
On top of the cell B is deposited a BSF layer 114 which performs the same function as the BSF layer 109. A p++/n++ tunnel diode 115 is deposited over the BSF layer 114 similar to the layers 110, again forming a circuit element to connect subcell B to subcell C.
A barrier layer 116a, preferably composed of InGa(Al)P, is deposited over the tunnel diode 115, to a thickness of about 1.0 micron. Such barrier layer is intended to prevent threading dislocations from propagating, either opposite to the direction of growth into the middle and top subcells B and C, or in the direction of growth into the bottom subcell A, and are more particularly described in US 2009/0078309 A1 .
A metamorphic layer (grading interlayer) 116 is deposited over the barrier layer 116a. Layer 116 is preferably a compositionally step-graded series of InGaAlAs layers with monotonically changing lattice constant that is intended to achieve a transition in lattice constant from subcell B to subcell C. The band gap of layer 116 is preferably 1.5 ev consistent with a value slightly greater than the band gap of the middle subcell B.
In one embodiment, as suggested in the Wanless et al. paper, the step grade contains nine compositionally graded InGaP steps with each step layer having a thickness of 0.25 micron. In the preferred embodiment, the layer 116 is composed of InGaAlAs, with monotonically changing lattice constant.
In another embodiment of the present invention, an optional second barrier layer 116b may be deposited over the InGaAlAs metamorphic layer 116. The second barrier layer 116b will typically have a slightly different composition than that of barrier layer 116a.
A window layer 117 is deposited over the barrier layer 116b, this window layer operating to reduce the recombination loss in subcell "C". It should be apparent to one skilled in the art that additional layers may be added or deleted in the cell structure without departing from the scope of the present invention.
On top of the window layer 117, the layers of cell C are deposited: the n+ emitter layer 118, and the p-type base layer 119. These layers are preferably composed of InGaAs, although an other suitable materials consistent with lattice constant and band gap requirements may be used as well.
A BSF layer 120 is deposited on top of the cell C, the BSF layer performing the same function as the BSF layers 109 and 114.
Finally a p+ contact layer 121 is deposited on the BSF layer 120.
It should be apparent to one skilled in the art, that additional layer(s) may be added or deleted in the cell structure without departing from the scope of the present invention.
FIG. 2 is a cross-sectional view of the solar cell of FIG. 1 after the next process step in which a metal contact layer 122 is deposited over the p+ semiconductor contact layer 121. The metal is preferably Ti/Au/Ag/Au.
FIG. 3 is a cross-sectional view of the solar cell of FIG. 2 after the next process step in which an adhesive layer 123 is deposited over the metal layer 122. The adhesive is preferably Wafer Bond (manufactured by Brewer Science, Inc. of Rolla, MO.).
FIG. 4 is a cross-sectional view of the solar cell of FIG. 3 after the next process step in which a surrogate substrate 124, preferably sapphire, is attached. The surrogate substrate is about 40 mils (1.016 mm) in thickness, and is perforated with holes about 1 mm in diameter, spaced 4 mm apart, to aid in subsequent removal of the adhesive and the substrate.
FIG. 5A is a cross-sectional view of the solar cell of FIG. 4 after the next process step in which the original substrate is removed by a sequence of lapping and/or etching steps in which the substrate 101, the buffer layer 103, and the etch stop layer 104, are removed. The choice of a particular etchant is growth substrate dependent.
FIG. 5B is a cross-sectional view of the solar cell of FIG. 5A with the orientation with the surrogate substrate 124 being at the bottom of the Figure. Subsequent Figures in this application will assume such orientation.
FIG. 6A is a top plan view of a wafer in which for solar cells are implemented. The depiction of four cells is for illustration for purposes only, and the present invention is not limited to any specific number of cells per wafer.
In each cell there are grid lines 501 (more particularly shown in cross-section in FIG. 10), an interconnecting bus line 502, and a contact pad 503. The geometry and number of grid and bus lines is illustrative and the present invention is not limited to the illustrated embodiment.
FIG. 6B is a bottom plan view of the wafer with four solar cells shown in FIG. 6A.
FIG. 7 is a top plan view of the wafer of FIG. 6A after the next process step in which a mesa 510 is etched around the periphery of each cell using phosphide and arsenide etchants.
FIG. 8 is a simplified cross-sectional view of the solar cell of FIG. 5B depicting just a few of the top layers and lower layers over the surrogate substrate 124.
FIG. 9 is a cross-sectional view of the solar cell of FIG. 8 after the next process step in which the etch stop layer 104 is removed by a HCl/H₂O solution.
FIG. 10 is a cross-sectional view of the solar cell of FIG. 9 after the next sequence of process steps in which a photoresist mask (not shown) is placed over the contact layer 105 to form the grid lines 501. The grid lines 501 are deposited via evaporation and lithographically patterned and deposited over the contact layer 105. The mask is lifted off to form the metal grid lines 501.
FIG. 11 is a cross-sectional view of the solar cell of FIG. 10 after the next process step in which the grid lines are used as a mask to etch down the surface to the window layer 106 using a citric acid/peroxide etching mixture.
FIG. 12 is a cross-sectional view of the solar cell of FIG. 11 after the next process step in which an antireflective (ARC) dielectric coating layer 130 is applied over the entire surface of the "bottom" side of the wafer with the grid lines 501.
FIG. 13 is a cross-sectional view of the solar cell of FIG. 12 after the next process step in which the mesa 510 is etched down to the metal layer 122 using phosphide and arsenide etchants. The cross-section in the figure is depicted as seen from the A-A plane shown in FIG. 7. One or more silver electrodes are then welded to the contact pad(s).
FIG. 14 is a cross-sectional view of the solar cell of FIG. 13 after the next process step after the surrogate substrate 124 and adhesive 123 are removed by EKC 922. The preferred perforations provided in the surrogate substrate have a diameter of 0.033 inches (0.8382 mm), and are separated by 0.152 inches (3.8608 mm).
FIG. 15 is a cross-sectional view of the solar cell of FIG. 14 In one embodiment after the next process step in which an adhesive is applied over the ARC layer 130 and a rigid coverglass attached thereto.
In a different embodiment, the solar cell of FIG. 13 may be initially mounted on a support, and the surrogate substrate 124 and adhesive 123 subsequently removed. Such a support may be the rigid coverglass mounted by an adhesive, as depicted in FIG. 15.
FIG. 16 is a graph of the doping profile between the emitter and base layer in a subcell of a metamorphic solar cell not forming part of the present invention.
The specific doping profile according to the present invention is that the emitter doping decreases from approximately 5 x 10¹⁸ per cubic centimeter in the region immediately adjacent the adjoining layer (e.g. layers 106, 111, or 117) to 5 x 10¹⁷ per cubic centimeter in the region adjacent the p-n junction. The base doping increases exponentially from 1 x 10¹⁶ per cubic centimeter adjacent the p-n junction to 1 x 10¹⁸ per cubic centimeter adjacent the adjoining layer (e.g., layer 109, 114, or 120).
The absolute value of the collection field generated by an exponential doping gradient exp[-x/λ] is given by the constant electric field of magnitude E = (kT/q(1/λ))(exp[-χ_b /λ]), where k is the Boltzmann constant, T is the absolute temperature in degrees Kelvin, q is the absolute value of electronic charge, and λ is a parameter characteristic of the doping decay.
The efficacy of the present invention has been demonstrated in a test solar cell which incorporated an exponential doping profile in the 3µm thick base layer of the bottom subcell, according to the present invention. Following measurements of the electrical parameters of the test cell, there was observed a 6.7% increase in current collection. The measurements indicated an open circuit voltage (V_oc) equal to at least 3.014V, a short circuit current (J_sc) of at least 16.55 mA/cm, and a fill factor (FF) of at least 0.86 at AMO.
The exponential doping profile taught by the present invention produces a constant field in the doped region. In the particular triple junction solar cell materials and structure of the present invention, the bottom cell has the smallest short circuit current among all the subcells. In a triple junction solar cell, the individual subcells are stacked and form a series circuit. The total current flow in the entire cell is therefore limited by the smallest current produced in any one of the subcells. Thus, by increasing the short circuit current in the bottom cell by 6.7%, the current more closely approximates that of the higher subcells, and the overall efficiency of the triple junction solar cell is increased by 6.7% as well. In a solar triple junction cell with approximately 30% efficiency, the implementation of the present invention would increase efficiency by a factor of 1.067, i.e. to 32.01%. Such an increase in overall efficiency is substantial in the field of solar cell technology. In addition to an increase in efficiency, the collection field created by the exponential doping profile will enhance the radiation hardness of the solar cell, which is important for spacecraft applications.
Although the exponentially doped profile is the doping design which has been implemented and verified, other doping profiles may give rise to a linear varying collection field which may offer yet other advantages. For example, a doping profile of e ^{-x 2/λ 2} produces a linear field in the doped region which would be advantageous for both minority carrier collection and for radiation hardness at the end-of-life of the solar cell. Such other doping profiles in one or more base layer are within the scope of the present invention.
The doping profiles depicted herein are merely illustrative, and other more complex profiles may be utilized as would be apparent to those skilled in the art without departing from the scope of the present invention.
It will be understood that each of the elements described above, or two or more together, also may find a useful application in other types of constructions differing from the types of constructions differing from the types described above.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.

Claims

A method of forming a multijunction solar cell comprising an upper subcell (A), a middle subcell (B), and a lower or bottom subcell (C), the method comprising:
providing a first substrate (101) for the epitaxial growth of semiconductor material;

forming a first solar subcell (A) having a base (108) and an emitter layer (107) on said substrate (101) having a first band gap;

forming a second solar subcell (B) having a base (113) and an emitter layer (112) over said first solar subcell (A) having a second band gap smaller than said first band gap;

forming a grading interlayer (116) over said second solar subcell (B), said grading interlayer (116) having a third band gap greater than said second band gap; and

forming a third solar subcell (C) having a base (119) and an emitter layer (118) over said grading interlayer (116) having a fourth band gap smaller than said second band gap such that said third subcell (C) is lattice mis-matched with respect to said second subcell (B),

characterised in that

at least one of the bases (108, 113, 119) has an exponentially doped profile, and

wherein the base (119) in said third solar subcell (C) has an exponential gradation in doping from 1 x 10¹⁶ per cubic centimeter adjacent the base-emitter junction to 1 x 10¹⁸ per cubic centimeter adjacent an adjoining layer(120).
A method as defined in claim 1, wherein the base (113) in said second solar subcell (B) has an exponential gradation in doping from 1 x 10¹⁶ per cubic centimeter adjacent the base-emitter junction to 1 x 10¹⁸ per cubic centimeter adjacent an adjoining layer (114).
A method as defined in claim 1, wherein the base (108) in said first solar subcell (A) has an exponential gradation in doping from 1 x 10¹⁶ per cubic centimeter adjacent the base-emitter junction to 1 x 10¹⁸ per cubic centimeter adjacent an adjoining layer (109).
A method as defined in claim 1, wherein the emitter layer (107, 112, 118) in at least one of the solar subcells (A, B, C) has an increasing gradation in doping from 5 x 10¹⁷ per cubic centimeter adjacent the base-emitter junction to 5 x 10¹⁸ per cubic centimeter adjacent an adjoining layer (106, 111, 117).
A method as defined in claim 3, wherein said third solar subcell (C) is the bottom subcell and the exponential gradation in doping results in an increase in short circuit current to a level approximately equal to the short circuit current in a higher subcell.
A method as defined in claim 1, wherein said first substrate is composed of GaAs.
A method as defined in claim 1, wherein said first solar subcell (A) is composed of an InGa(Al)P emitter region and an InGa(Al)P base region.
A method as defined in claim 1, wherein said second solar subcell (B) is composed of an InGaP emitter region and an GaAs base region.
A method as defined in claim 1, wherein said grading interlayer (116) is composed of InGaAIAs, preferably of nine steps of layers with monotonically changing lattice constant.
A method as defined in claim 1, wherein said third solar subcell (C)is composed of InGaAs, preferably, further comprising depositing a barrier layer (116a; 116b) about 1 µm (one micron) in thickness adjacent said grading interlayer (116) for preventing threading dislocations from propagating.
A method of manufacturing a solar cell according to claim 1, comprising:
providing the first substrate (101);

depositing on said first substrate (101) a sequence of layers (102-122) of semiconductor material forming a solar cell including at least one base layer (108, 113, 119) with exponential doping;

mounting a surrogate substrate (124) on top of the sequence of layers (102-122), and

removing the first substrate (101).
A method as defined in claim 11, wherein the sequence of layers (102-122) of semiconductor material forms a triple junction solar cell, including first, second and third solar subcells (A, B, C), and preferably further comprising removing the surrogate substrate (124) and mounting the solar cell on a support.